Process of producing sulphonyl chlorides



Patented June 20, 1944 I PROCESS OF PRODUCING SULPHONYL CHLORIDES Arthur Lawrenc e Fox, Easton, Pa., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 11, 1943,

. Serial No. 478,834

Claims.

This invention relates to new chemical compounds and processes' and more particularly to alkyl substituted aromatic compounds which contain an exo-sulphonyl chloride group or an 2,321,022 on June 8, 1943.

This invention has as an object the preparation of new surface ,active compounds and intermediates therefor. A further object is to prepare these new compounds by a novel and easily conducte process which gives good yields of relatively high quality products. A still further object is to employ these new compounds in various technicalapplications. Other objects will appear hereinafter.

These objects are accomplished by the following invention in accordance with which new alkyl substituted aromatic compounds which contain an exo-sulphonyl chloride group or an exo-sulphonyl group are produced. In these new compounds there is present an'alkyl group which contains at least 5 carbon atoms. The preferred compounds of this invention are those in which an alkyl group contains or more carbonvatoms or at least two alkyl groups each contain 5 or more carbon atoms. These preferred compounds exhibit much greater surface activity than compounds which contain a total of less than 10 carbon atoms in the alkyl substituent or substituents. The aromatic portion of these compounds is preferably an aromatic hydrocarbon nucleus and more especially an aromatic hydrocarbon nucleus of the benzene and naphthalene series. The exo-sulphonate group in these new comopounds has the general formula SOaM ture of compounds containing sulphonyl chloride groups in the side chain. The yields depend somewhat on the length of the side chain, the longer the alkyl chain the greater being the yields under normal circumstances.

Products of this type or those derived therefrom are useful in many of the arts, for example, for producing textile assistants, such as wetting agents, detergents, softening agents, waterproofing agents and'the like, and they are also of interest for the production of dyestufl intermediates, such as are obtained by nitration of the aromatic nucleus followed by reduction of the nitro group. This process oflers a practical method of obtaining exo-sulphonated alkyl aromatic hydrocarbons in good yields.

The term exo" as used in this application is employed in the sense that it is used in the second edition of Webster's New International Dictionary to denote a group which is in the side chain and not in the ring of an alkyl aromatic compound.

The following example illustrates but does not limit this invention. All parts are given by weight.

EwampleTriamyl benzene era-sodium sulphonate 144 parts of triamyl-benzene and 100 parts of benzene were mixed and warmed to -55 C. in the presence of actinic light from a tungsten filament lamp. Then one part of pyridine was added and parts of sulphuryl chloride was gradually introduced over a period of 50 minutes. After maintaining the temperature another 1.5 hours at 50-55 C., one part of pyridine was added and the reaction mass maintained at 50 55 C. for 16 hours. Then another part of pyridine was added and the reaction continued 6 hours more. The benzene and unreacted sulphuryl chloride were removed at YO- C. under vacuum, and 1'75 parts of a red brown oil was obtained. On hydrolysis with sodium hydroxide this gave triamylbenzene exo-sodium sulphonate which showed excellent soft water detergency, moderate hard water detergency, and gave a wetting speed of 25 seconds at a concentration of 1 gram active ingredient per liter when tested by the method of Draves and Clarkson which is described in American Dyestuffs Reporter 20, 201 (1931).

The temperature at which the reaction is run may vary widely. The reaction is usually carried out at temperatures at which all reactants are liquid. The temperature should not be willciently low to cause freezing of the reactants or high enough to cause decomposition of the sulphohyl chlorides which are being formed. The preferred temperature range is 20 to 80 C.

In accordance with the procedure exemplified in the preceding example other alkyl substituted aromatic compounds containing at least carbon atoms in an alkylv chain may be reacted with sulphuryl chloride to produce alkyl substituted aromatic compounds-that contain an exo- V sulphonyl chloride group or an exo-sulphonate group. Among the alkyl substituted aromatic compounds that may be reacted with sulphuryl chloride in accordance with this invention there may be mentioned hexyl benzene, octyl benzene, decyl benzene, decyl xylene, dodecyl benzene, tridecyl' benzene, hexadecyl benzene, octyl naphthalene, decyl naphthalene, dodecyl naphtha-v lene, etc. Mixtures of alkylated compounds such as may be obtained by condensing chlorinated kerosenes or white oils with aromatic hydrocarbons, such as benzene, toluene, or naphthalene, by means of a Friedel-Crafts reaction may also be converted to compounds containing an exosulphonyl chloride group or an exosulphonate group in accordance with this inven tion. Polyalkylated aromatic compounds such as trlamyl benzene, tetraamyi benzene, dioctyl benzene, didecyl benzene, didodecyl benzene, ditridecyl benzene, diam-yl naphthalene, triamyl naphthalene, dioctyl naphthalene, didodecyl naphthalene, etc., are also contemplated reactants for use in the presentinvention.

. Other aromatic nuclei than benzene and naphthalene are also contemplated. Thus, alkyl anthracenes, alkyl phenanthrenes, alkyl carbazoles, etc. may be converted to exo-sulphonates in this manner. Furthermore, the aromatic. nucleus may contain substituents which themselves do not react with sulphuryl chloride, and hence compounds such as alkyl chlorobenzenes, alkyl benzoic acids, alkyl anthraquinones and alkyl nitro naphthalenes may also be used. It is to be understood that the alkyl compounds mentungsten filament lamp has been'sp ecifled. Thisdiamine,

diamine, N-dimethyl C dimethylglycinenitrile,

oxide, dimethylaniline, m-nitrodimethylanilinc, isoamylamine, tributylamine, N-dimethyl cycle hexylamine, ethylenediamine, octadecylamine, hexamethylenediamine, uns.-'dimethylethylene- N,N,N',N'-tetramethylhexamethylenetetramethylammoniumformate, N,N'-disalicylaldiaminoethane, N (Z-ethylhexanylidine) -2-ethylhexylamine, 2 amino- 2 methylpropanol 1, dodecyl carbamate, butyrolactam, xylylheptadecylketoxime, hexamethylenediisocyanate, methallylisothiocyanate, acetamide, N-dimethylmethsulphide, thiophenol, triphenylphosphine, phenylethyleneoxide, and potassium anthraquinonel-sulphonate.

Instead of using sodium hydroxide to hydrolyze the sulphonyl chlorides I may employ aqueous solutions of potassium hydroxide, so'dium caris merely because it ofiers a convenient source of actinic light and not because it produces a predominant quantity of the efiective wave length. Other sources of actinic light such as. mercury arc, carbon arc, neon lights, fluorescent lights, direct or diffused sunlight or any other source providing wave lengths promoting this reactionmay be used. Some of these light sources are'superior to tungsten filament lamps.

In addition to light it is preferable to use a. catalyst such as pyridine. In place of pyridine,

I may use other heterocyclic compounds containing nitrogen in the ring such as quinoline, quinaldine, nicotine, alpha-aminopyridine 2,6-dibonate, potassium acetate, ammonium hydroxide, quaternary ammonium hydroxides, methyl amine, dimethyl amine, trimethyl amine, ethanol amine, diethanol amine, triethanol amine, diethanol aniline, pyridine, piperidine, or other similar alkaline reacting compounds.

The above description and example .are intended to be illustrative only'and not 'to limit the scope of the invention. Any departure therefrom which conforms to the spirit of-the invention is intended to be' included within the scope of the appended claimsij j .Iclaimy g 1.' A process of making an alkyl substituted aromatic compound-which contains an exo-sulphonyl chloride group which comprises reacting an alkyl substituted aromatic compound wherein an alkyl group containsat least 5 carbon atoms with, sulphuryl chloride in-the presence of actinic light and a heterocyclic compound containingnitrogen in the ring.

2. A process-as defined in claim 1 according i to which the exo-sulphonyl chloride group is aminopyridine, phenanthroline, piperidine, isoquinoline, nicotinic amide, morpholine, pyridinium acethydrazide, Z-mercaptothiazoline, etc. The reaction may also be catalyzed by using still other compounds in place of or in addition to a' heterocyclic compound containing nitrogen in the ring. Other compounds which are known to thionyl chloride, sulphur, chlorine, carbon monconverted by' hydrolysis to an exo-sulphonate group. I

3. A process of making an alkyl substituted aromatic hydrocarbon of the benzene and naphthalene series which contains an exocyclic sulphonyl chloride group which comprises reacting an alkyl substituted aromatic hydrocarbon of the benzene and naphthalene series wherein an alkyl group contains at least 5 carbon' atoms with sulphuryl chloride in the presence of actlnic light anda heterocyclic compound containing nitrogen in the'ring.

4. A process as defined in claim 3 in which the alkyl substituted aromatic 'hydrocarbonis triamyl benzene.

5. A process as defined in claim 3 in which the heterocyclic compound is pyridine.

ARTHUR LAWRENCE'FO'X.

our?" 4 CERTIFICATE OF CORRECTIQN. v Patent No. 2,551,6714... June 20, 191414..

ARTHUR LAWRFN GE FOX It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction asfollows': Page 1, first column, line 25, for "axe-sulphonyl" read --exo-sulphonate--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 8th day of August, A. D. 19%.

Leslie Frazer fiseal) Acting Commissioner of Patents.

CERTIFICATE on CORRECTION. Patent No. 2,351,671 June 20, 19141;.

AR'JHUR LAWRENCE FOX.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring eorrection as follows: Paige 1, first column, line 25, for "exo-sulphonyl read --exo-sulphona.te--; and that the said Letters Patent should be read with this correction therein that the same may confonn to the record of the case in the Patent Office.

Signed and sealed this 8th day of August, A. D. 19%.

Leslie Frazer (,SealY Acting Commissioner of Patents. 

